Nihms653547 PEEK

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Acta Biomater. Author manuscript; available in PMC 2016 February 01.
Published in final edited form as:
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Acta Biomater. 2015 February ; 13: 159–167. doi:10.1016/j.actbio.2014.11.030.
High strength, surface porous polyether-ether-ketone for load-

bearing orthopaedic implants
Nathan T. Evans†,*,a, F. Brennan Torstrick†,b,c, Christopher S.D. Leed, Kenneth M. Duponte,
David L. Safranskie, W. Allen Changd, Annie E. Macedof, Angela Linb,c, Jennifer M.
Boothbyf, Daniel C. Whittingslowf, Robert A. Carsonb, Robert E. Guldbergb,c, and Ken
Galla,b,c
F. Brennan Torstrick: brennan@gatech.edu; Christopher S.D. Lee: chris.lee@verteraspine.com; Kenneth M. Dupont:
kenneth.dupont@medshape.com; David L. Safranski: david.safranski@medshape.com; W. Allen Chang:
allen.chang@verteraspine.com; Annie E. Macedo: amacedo@gatech.edu; Angela Lin: angela.lin@me.gatech.edu;
Jennifer M. Boothby: jboothby3@gatech.edu; Daniel C. Whittingslow: dwhittingslow@gatech.edu; Robert A. Carson:
robert.carson@gatech.edu; Robert E. Guldberg: robert.guldberg@ibb.gatech.edu; Ken Gall: ken.gall@mse.gatech.edu
aSchool of Materials Science and Engineering, 771 Ferst Drive, J. Erskine Love Building, Georgia
Institute of Technology, Atlanta, GA 30332

bGeorge W. Woodruff School of Mechanical Engineering, 801 Ferst Drive, Georgia Institute of
Technology, Atlanta, GA 30332
cParkerH. Petit Institute for Bioengineering and Bioscience, 315 Ferst Drive, Georgia Institute of
Technology, Atlanta, GA 30332
dVertera, Inc., 311 Ferst Drive NW Suite L1328, Atlanta, GA 30332
eMedShape, Inc., 1575 Northside Drive, NW, Suite 440, Atlanta, GA 30318
fWallaceH. Coulter Department of Biomedical Engineering, 313 Ferst Drive, Georgia Institute of
Technology and Emory University, Atlanta, GA 30332
Abstract
Despite its widespread clinical use in load-bearing orthopaedic implants, polyether-ether-ketone
(PEEK) is often associated with poor osseointegration. In this study, a surface porous PEEK
material (PEEK-SP) was created using a melt extrusion technique. The porous layer thickness was
399.6±63.3 µm and possessed a mean pore size of 279.9±31.6 µm, strut spacing of 186.8±55.5
µm, porosity of 67.3±3.1%, and interconnectivity of 99.9±0.1%. Monotonic tensile tests showed
that PEEK-SP preserved 73.9% of the strength (71.06±2.17 MPa) and 73.4% of the elastic
modulus (2.45±0.31 GPa) of as-received, injection molded PEEK. PEEK-SP further demonstrated
© 2014 Elsevier Ltd. All rights reserved.

*
Corresponding Author, Contact Information:, Evans: nevans3@gatech.edu, 404-660-4418.
†These authors contributed equally to this work.
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Disclosures
K.M.D and D.L.S are employees of MedShape, Inc. and C.S.D.L., K.M.D, D.L.S, K.G. own stock/stock options in MedShape, Inc.
C.S.D.L. and W.A.C. are employees of Vertera, Inc. and N.T.E., F.B.T. C.S.D.L., W.A.C., K.M.D., D.L.S., D.C.W., R.E.G., and K.G.
own stock/stock options in Vertera, Inc.
Evans et al. Page 2
a fatigue strength of 60.0 MPa at one million cycles, preserving 73.4% of the fatigue resistance of
injection molded PEEK. Interfacial shear testing showed the pore layer shear strength to be
23.96±2.26 MPa. An osseointegration model in the rat revealed substantial bone formation within
the pore layer at 6 and 12 weeks via µCT and histological evaluation. Ingrown bone was more
closely apposed to the pore wall and fibrous tissue growth was reduced in PEEK-SP when
compared to non-porous PEEK controls. These results indicate that PEEK-SP could provide
improved osseointegration while maintaining the structural integrity necessary for load-bearing
orthopaedic applications.
Keywords
polyetheretherketone (PEEK); fatigue; surface porous; orthopaedic implant
1. Introduction
The ultimate goal of most medical implants is to restore impaired biological function and
achieve functional integration with the body. Several porous polymers and other tissue
engineered scaffolds have made advances in this regard for many soft tissue applications
where mechanical loading is minimal [1]. However, similar solutions in high load-bearing
orthopaedic environments remain elusive due to performance tradeoffs in clinically adopted
biomaterials. Metallic implants provide high strength but are associated with medical
imaging artifacts and unwanted bone resorption due to their high modulus and
corresponding stress shielding [2]. Current porous polymer scaffolds can facilitate bony
ingrowth but lack the strength necessary for high load-bearing environments experienced in
clinical soft tissue reconstructions, spinal fusions, and arthrodesis applications [3, 4].
Bioresorbable polymers and composites facilitate osseointegration and implant resorption,
but are clinically limited to soft tissue reconstructions and have cited incidences of
prolonged inflammation, migration, incomplete degradation, and implant breakage [5].
As a relatively new implant material, polyether-ether-ketone (PEEK) has gained widespread

acceptance as a high-strength polymer used primarily in spinal fusions and soft tissue
reconstructions, with favorable imaging compatibility and stiffness that closely matches
bone [6, 7]. However, PEEK suffers a key property tradeoff in poor osseointegration. Its
aromatic backbone and semi-crystalline nature provide high strength and biocompatibility,
yet its hydrophobic and chemically inert surface limits local bone attachment [8, 9].
Basic research approaches to enhance PEEK osseointegration have focused both on surface
modification and bulk porosity. Surface modifications such as plasma or chemical etching
[10–12], addition of bioactive coatings [13, 14], and PEEK composites have performed well
in vitro and in vivo [15], yet their clinical success may be limited due to their potential
instability and delamination in physiological or surgical environments [16, 17]. Introducing
bulk porosity throughout PEEK implants via powder sintering (or compression molding)
aims to increase implant fixation by encouraging the migration and proliferation of various
cell types to enhance vascular and bone tissue ingrowth [3, 18]. Indeed, porous PEEK
implants have exhibited increased osseointegration [15]; however, they also suffered up to

Evans et al. Page 3
86% reduction in strength due to the high overall fraction of porosity and the relatively weak
local bonds created during powder sintering [3, 19, 20].
Limiting porosity to PEEK’s surface could promote osseointegration and maintain bulk
mechanical properties [19]. Furthermore, a surface porosity approach is supported by the
finding that a completely porous structure may not be required for functional integration [19,
21]. A porous surface layer could retain implant strength, provide an adequate conduit for
bone ingrowth, and avoid tissue necrosis common at the center of large fully porous
implants in cases of limited vascular and nutrient supply [22, 23].
Here we investigate a novel method to create a functionally graded PEEK material with a
balance between surface porosity for osseointegration and a solid core for mechanical load-
bearing. Porous and solid regions are seamlessly connected, resulting in outstanding
mechanical properties compared to powder sintering or coatings [3]. Samples are created
using a patent-pending technique in which PEEK is extruded through sodium chloride
crystals to create a surface porosity. The resulting structure and properties of the surface
porous PEEK are discussed as well as preliminary in vivo results to provide initial insight
into its potential to osseointegrate.
2. Materials and Methods

2.1 Sample Preparation
Surface porous PEEK (PEEK-SP) samples were created by extruding medical grade PEEK
(Zeniva® 500, Solvay Advanced Polymers, Tm=340°C) through the lattice spacing of
sodium chloride crystals (Sigma Aldrich) under heat and pressure. After cooling, embedded
sodium chloride crystals were leached in water leaving behind a porous surface layer. To
control for pore size, sodium chloride was sieved into a range of 200–312 µm using #50 and
#70 U.S. mesh sieves. Injection molded PEEK samples (PEEK) were used as smooth
controls. Powder sintered bulk porous samples (PEEK-BP) were created using a
compression molding technique [6]. Briefly, sodium chloride and PEEK powder
(KetaSpire® KT-820FP, Solvay Advanced Polymers) were thoroughly mixed at a ratio to
achieve equivalent pore size and porosity as PEEK-SP. Powder mixtures were sintered
under 260 MPa compression for 60 minutes at 363°C within a 10 mm diameter cylindrical
mold (Heated Manual Press, Model 4386, Carver, Inc.). Sodium chloride was leached in
water and sodium chloride removal was confirmed via microcomputed tomography (µCT).
Poly(methyl methacrylate) (PMMA, McMaster-Carr), a polymer commonly used as bone
cement in orthopaedic surgery, was used as a control for monotonic tension and tensile
fatigue studies.
All tensile specimens were ASTM D638 Type I dog-bone samples. Shear samples were cut
from PEEK bars to have a cross-sectional shear area of 16×16 mm for PEEK and PEEK-SP
or 10 mm diameter for PEEK-BP. In vivo implants were 5 mm diameter cylinders machined
to a length of 8 mm from PEEK bars. One face was made surface porous while the other
face was machined smooth as a control. A hole was bored through the center to replace the
native medullary cavity.

Evans et al. Page 4
2.2 Pore Layer Characterization

PEEK-SP samples were cut to size and the porous layers were scanned using µCT (µCT 50;
Scanco Medical) at 10 µm voxel resolution with the scanner set at a voltage of 55 kVp and a
current of 200 µA (n=15). Surface porous layers were manually contoured tightly to the
pores to minimize inclusion of non-porous volume. A global threshold was applied to
segment PEEK from pore space and kept consistent throughout all evaluations. Pore layer
morphometrics were evaluated using direct distance transformation methods [24]. Briefly,
strut spacing was calculated using a maximal spheres method adapted from a trabecular
spacing index. Porosity was determined by 1–BV/TV, where BV represented polymer
volume and TV represented the total volume of the porous layer. Average pore layer
thickness was determined using a trabecular thickness index algorithm on the filled TV of
each porous layer. Pore layer interconnectivity was determined by inverting segmented pore
and solid spaces and dividing the largest connected pore space volume by the total pore
volume [25]. Scanning electron microscopy (SEM, Hitachi S-3700N VP-SEM) was utilized
to observe the surface topography of PEEK-SP samples. Pore size was measured from SEM
images as the length of the pore diagonal (n=50).
To detect changes in molecular weight due to PEEK-SP processing, gel permeation

chromatography (GPC) was performed by Solvay Advanced Polymers on 100 mg samples

of the isolated surface porous layer, solid core from a surface porous sample, and injection
molded PEEK.
2.3 Monotonic and Fatigue Tensile Testing

Tensile tests were performed according to ASTM D638 at room temperature using a MTS
Satec 20 kip (89 kN) servo-controlled, hydraulically-actuated test frame (n=5 PEEK-SP,
n=5 PEEK, n=4 PMMA). The crosshead speed was 50 mm/min. Force-displacement data
was used to calculate ultimate stress, elongation at break, and elastic modulus as well as
generate the stress-strain curves.
Fatigue tests were run at increasingly lower stresses below the ultimate stress of the samples
to generate S-N curves and determine the endurance limits of the respective samples.
Fatigue tests were run on the same Satec test frame in axial stress control at a frequency of 1
Hz with a sinusoidal load. Tests were run until failure or runout. Runout was defined as
greater than 1,000,000 cycles unless noted otherwise.
For monotonic and fatigue results, two representations of stress for PEEK-SP were
calculated: the first using load-bearing area, ALB, and the second using total area, AT (Fig.
1). Load-bearing area was taken as the cross sectional area of the as-received dog bone
before porous processing. Total area was taken as the cross sectional area of the dog bone
after porous processing. Use of total area produces stress values that assume void area
contributes to load-bearing, and results will consequently depend on pore layer thickness
and volume fraction of porosity. Conversely, load-bearing area includes only the cross-
sectional area of polymer material, including solid polymer and porous strut regions,
ignoring void area in the porous layer.

Evans et al. Page 5
2.4 Aligned Interfacial Shear

Interfacial shear testing was adapted from ASTM F1044-05 using 3M™ Scotch-weld™
2214 Non-Metallic Filled as adhesive and a 30 kN load cell (Instron). A thin layer of
adhesive was applied evenly to the surfaces of shear samples and like faces were pressed
together, clamped, and placed in a vacuum oven to cure at 121°C for 1 hour. The shear test
fixtures were clamped in Instron jaws and adjusted to enable horizontal alignment of the
shear sample. The plane of the adhesive was coincident with the axis of loading. Cured
samples were placed into custom fixtures ensuring a tight clearance fit. The fixtures were
pulled apart at 2.54 mm/min until the interfacial surfaces of the samples were completely
sheared. The shear stress was calculated based on the measured failure load and cross-
sectional area. Shear test groups included smooth PEEK (n=4), PEEK-SP (n=8) and PEEK-
BP (n=5).
2.5 Preliminary in vivo Animal Study

2.5.1 Surgery—An established rat femoral segmental defect model was utilized to
preliminarily assess the osseointegration potential of PEEK-SP compared to smooth PEEK
surfaces [26]. This model was chosen based on its previous use in characterizing bone
ingrowth in porous polymeric and metallic implants [27–30]. All surgical procedures were
approved by the Institutional Animal Care and Use Committee at the Georgia Institute of
Technology (IACUC protocol #A11028). Briefly, bilateral 8 mm femoral defects were made
in the central diaphyses of three 13-week old female Sasco Sprague-Dawley rats (Charles
River), totaling six defects. Femurs were stabilized prior to defect creation using a modular
plating system consisting of a polysulfone plate and two stainless steel risers. PEEK
implants with one surface porous and one smooth end face were press-fit into each defect
before incision closure (n=6). The orientations of surface porous faces were alternated
between contralateral limbs. After surgery animals were allowed to recover and ambulate
freely. Animals were injected with slow release buprenorphine at the time of surgery to
relieve any pain. One animal was euthanized at 6 weeks and the remaining two were
euthanized at 12 weeks.
2.5.2 Ex vivo µCT Imaging—Following euthanization, µCT scans were performed to

assess bone ingrowth into each face of the implant. Femurs were scanned at 55 kVp and 145
µA with a 15 µm voxel size (Viva-CT, Scanco Medical). Three-dimensional reconstructions
were created from two-dimensional slices thresholded to include mineral densities >50% of
native cortical bone.
2.5.3 Histology—Femoral explants were fixed in formalin and stored in 70% ethanol until
processing. Samples were processed through ascending grades of ethanol followed by
xylene before embedding in methyl methacrylate. After embedding, rough sections were cut
(Isomet® 1000 Precision Saw, Buehler) and then ground to 30 µm (EXAKT 400 CS).
Sections were stained using a Goldner’s Trichrome protocol to distinguish osteoid (red)
from mineralized bone (green).

Evans et al. Page 6
2.6 Statistical Analysis

Comparisons between the strength and modulus of PEEK-SP and solid PEEK were
performed with a Student’s t-test. The results of the interfacial shear test were analyzed
using a one-way ANOVA and Tukey post-hoc analysis (95% confidence interval). All data
is expressed as average±standard deviation.
3. Results
3.1 Pore Layer Characterization
Pore morphology reliably correlated to sodium chloride crystal size (200–312 µm) and cubic
nature with a pore size of 280±32 µm (Fig. 2). The pore layer was 67.3±3.1% porous and
highly interconnected (99.9±0.1%) with an average strut spacing of 186.8±55.5 µm as
determined by µCT. Interconnectivity values are potentially skewed slightly higher than
actual values due to spatial resolution imaging limitations that may have prevented detection
of thin walls between pores. However, pore interconnectivity was expected to be high due to
water’s high degree of pore accessibility during leaching, as evidenced by the absence of
residual sodium chloride on µCT. The average thickness of the pore layer was 399.6±63.3
µm.
Table 1 shows the molecular weight of the polymer from the surface porous region, a solid
region from a surface porous sample, and injection molded PEEK. The results demonstrate
that the surface porous processing does not change the molecular weight of the samples.
3.2 Tensile Monotonic Testing

The creation of a surface porosity did not significantly decrease the strength of samples
compared to injection molded controls when using ALB (p=0.52). The ultimate tensile
strength (σUTS) and elastic modulus of PEEK-SP samples were 96.11±2.61MPa and
3.36±0.30GPa compared to 97.7±1.0MPa and 3.34±0.14GPa for unprocessed solid PEEK
controls, respectively, using ALB (Fig. 3). However, failure strains were decreased from
20.24±2.43 to 7.79±2.25. When the total area was used in stress calculations, PEEK-SP
retained 73.9% of the strength and 73.4% of the elastic modulus of solid PEEK,
corresponding to a tensile strength of 71.06±2.17MPa and modulus of 2.45±0.31GPa for a
porous layer that comprises approximately 20% of the sample cross sectional area.
3.3 Tensile Fatigue Testing

PEEK-SP samples demonstrated high fatigue resistance regardless of which area was used
in stress calculations (σN = 60.0 MPa for ALB and σN = 45.3 MPa for AT) (Fig. 4). Further,
the fatigue strength of PEEK-SP (ALB) was 73% of the σUTS of smooth, injection-molded
PEEK. Both PEEK and PEEK-SP experienced higher fatigue strength at similar cycle
number than PMMA.
3.4 Aligned Interfacial Shear

The average shear strength of smooth PEEK, PEEK-SP, and PEEK-BP was 7.52±3.64,
23.96±2.26, and 6.81±0.81 MPa, respectively (Fig. 5). Different shear failure modes were
apparent for each group. Smooth PEEK failed at the glue layer interface, PEEK-SP failed

Evans et al. Page 7
within the porous network and within the solid region on the edges of some samples, and
PEEK-BP failed in the empty bulk porous region behind the glue layer.
3.5 Implant Osseointegration

Three-dimensional µCT reconstructions of PEEK explants at 6 and 12 weeks suggested bone
formation within the PEEK-SP network (Fig. 6). Bone ingrowth possessed cubic
morphology similar to that of the pores, suggesting most available pore space was occupied
by newly-formed bone. Cubic bone ingrowth regions were apparent at 4/6 porous interfaces
and 0/6 smooth interfaces. Bone growth through the central cannula and along the outer
surface of implants was present in 5/6 samples and originated from both proximal and distal
ends (data not shown). Quantitative evaluation of bone ingrowth was prevented due to
thresholding difficulties between PEEK and surrounding soft tissue.
Histological evidence confirmed that the mineral seen within pores on µCT reconstructions
was cellularized bone (Fig. 7). At both six and twelve weeks, substantial bone formation was
evident within the pore layer, with bone formation seeming to increase between the two time
points. Ingrown bone was closely apposed to the pore walls and exhibited a substantial
reduction in fibrous tissue formation compared to the smooth PEEK faces.
Qualitative agreement between µCT and histology was also confirmed by comparing bone
ingrowth morphology at approximately the same cross sections using each technique.
Mineral attenuation maps from µCT represented histological findings well and provided
further validation for using µCT to detect bone ingrowth into the PEEK-SP pore layer (Fig.
7).
4. Discussion
This study sought to create a surface porosity on PEEK to promote osseointegration while
maintaining the structural integrity necessary for high load-bearing orthopaedic implants.
The advantages of a surface porous polymeric implant have been previously discussed in the
literature [19, 31, 32]. However, no surface porous PEEK structure has been shown to
provide an adequate pore network for bone ingrowth while preserving the high strength of
PEEK.
Characterization of our PEEK-SP surface layer revealed pore size, porosity and
interconnectivity values that have been reported to allow for cell migration, nutrient
transport, and vascularization that contribute to successful bone-implant integration [19, 33].
We also show that PEEK-SP preserved a high degree of PEEK’s mechanical properties,
retaining over 70% of the strength and modulus of solid PEEK when total cross-sectional
area AT is used in the stress calculation. Comparatively, typical bulk porous (BP) polymers
reported in the literature retain only 15–36% strength and 11–39% modulus of the
unprocessed polymer, depending on porous volume fraction (Fig. 8) [3, 20, 33–38].
Although the measured strength of PEEK-SP is decreased when using the total cross-
sectional area AT, the creation of a surface porosity does not significantly decrease the
strength when calculated with the load-bearing area ALB (Fig. 3). The results indicate that

Evans et al. Page 8
the stress concentration effect of pores does not negatively impact material strength. The
results also indicate that PEEK-SP retains its specific strength (strength/density), meaning
the introduction of porosity using this processing method only spreads the material out
rather than inherently weakening it. In addition, PEEK-SP possesses mechanical properties
within the range of trabecular and cortical bone (Fig. 8), a characteristic that has been
suggested to improve in vivo functionality [33]. Mechanical properties can be tuned further
by adjusting implant design parameters, such as decreasing layer thickness
Given the decrease in ductility in PEEK-SP and the inherent cyclic loading experienced by
orthopaedic implants, it was important to evaluate the effect of the processing on the fatigue
properties of PEEK. As shown in Fig. 4, the inherent fatigue resistance of solid PEEK was
highly maintained after creation of a porous surface layer. The data also demonstrate that the
fatigue resistance of PEEK-SP outperformed other clinically used orthopaedic biomaterials.
PMMA, a polymer used as bone cement, did not trend towards an endurance limit and
possessed much lower fatigue strength than PEEK-SP in the high cycle regime. Similarly,
porous tantalum, a bulk porous metallic implant material used clinically to facilitate
osseointegration, has fatigue performance almost 43% lower than surface porous PEEK at
similar cycle number [39].
Because large shear stresses are experienced near bone-implant interfaces in vivo that can
lead to micro-motion and implant loosening [40], it was essential to probe the inherent
interfacial shear strength of the porous surface layer. The significant increase in interfacial
shear strength of PEEK-SP compared with solid (smooth) PEEK suggests that PEEK-SP
will possess the advantage of a mechanical interlock and higher bonding strength between
the implant biomaterial and the surrounding natural bone once ingrowth occurs, providing
greater mechanical stability at this critical interface [41]. Furthermore, PEEK-SP provides
this advantage over many current techniques explored in the literature. Physical surface
treatments such as plasma modification have shown increased bioactivity of PEEK implants
but may not provide sufficient space for bony ingrowth and implant-bone fixation [11, 14].
In addition, PEEK implant coatings such as titanium and hydroxyapatite have demonstrated
improved cellular response, [13, 42] but can be subject to delamination and decreased
fatigue life [43]. Finally, sulfonation has been used to chemically modify the surface of
PEEK and introduce a nanoporous surface network to improve osseointegration [32].
However, with single-micron pores that are well below the typical range for bone formation,
sulfonated surface porous PEEK may not allow for the bony ingrowth that contributes to a
strong mechanical interlock between the implant and bone.
The process of creating a surface porosity on PEEK implants introduces a random,

topographically varied surface that may contribute to enhanced osseointegration. Such a
disordered topography has been shown to improve the osteogenic response at nano- to
micron-size scales [44–47]. At a larger scale, porosity has also shown increased
osteogenesis compared to solid or topographically smooth surfaces [33]. Together, the
literature suggests that the random, topographically varied PEEK-SP surface may enhance
the cellular response, leading to more stable fixation than PEEK that is smoother at the
cellular level.

Evans et al. Page 9
Though PEEK-SP and PEEK-BP both offer the potential for bone ingrowth into the porous
network, the significantly lower shear strength of PEEK-BP may limit its clinical use in
rigorous loading environments. The three-fold higher shear strength of PEEK-SP could be
attributed to the porous surface layer being extruded from the bulk material instead of being
created with the additive or sintering techniques currently used to create PEEK-BP.
Extrusion of PEEK-SP from the bulk material seamlessly integrates solid and porous regions
at the molecular level and maintains the high molecular weight necessary for high strength
(Table 1). Notably, the surface porous layer has higher interfacial shear strength than
trabecular bone [48] (Fig. 5), which implies that failure will originate from bone itself and
not the solid-porous interface even when high quality bone has fully integrated.
Preliminary in vivo results provide further evidence of PEEK-SP’s capacity to promote bony
ingrowth needed for strong implant fixation (Fig. 6, 7). Substantial bone formation within
the pore layer was confirmed via µCT and histology at six and twelve weeks post-surgery.
These initial in vivo results compare favorably with previously reported porous networks
with similar architectures to PEEK-SP. For example, a porous PEEK-HA composite has
been shown to facilitate bone ingrowth with close apposition to the pore walls, similar to
PEEK-SP [49]. However, even the nonporous form of current PEEK-HA composites can
lack the strength, ductility and fatigue resistance of PEEK-SP.
A direct comparison of PEEK-SP to porous titanium can be found in a study that used a
nearly identical segmental defect model in the rat [27]. This study reports a time course of
bone ingrowth close to that of PEEK-SP and also describes similar histological findings.
Both studies found substantial bone formation in the central cannula and around the outside
of the implants, illustrating an attempt by bone to bridge the defect. Both studies also found
close bone apposition to the pore walls (or struts) with the presence of some fibrous tissue in
regions where bone was absent.
Though some fibrous tissue formation was apparent within the PEEK-SP pore network, the
degree to which it formed was reduced compared to the characteristic fibrous encapsulation
of smooth PEEK seen in Fig. 7 and in previous studies [50, 51]. Many regions of PEEK-SP
possessed pores that were completely filled with cellularized bone and no fibrous layer was
observed between the bone and implant. Such reduced fibrous encapsulation combined with
potentially faster bone ingrowth could increase implant stability and limit micromotion that
can lead to increased inflammation and eventual implant loosening and failure [45, 52, 53].
The clinical potential of PEEK-SP is further illustrated with the clearance of this technology
on a suture anchor implant through the Food and Drug Administration (FDA) in the United
States (marketed as Scoria™). Despite these promising preliminary findings, further work is
necessary to fundamentally understand what causes bone formation within the PEEK-SP
pore layer and the quantitative mechanics behind the osseointegration of PEEK-SP [54].
5. Conclusion
We have investigated a process for selectively introducing surface porosity on PEEK that
retains a substantial fraction of the solid polymer’s mechanical properties. This method

Evans et al. Page 10
provides many advantages over sintered bulk porous polymers that rely on superficial
bonding between polymer particles, which severely compromises mechanical properties.
The creation of a surface porosity produced samples with high tensile strength, fatigue
resistance and interfacial shear strength while simultaneously providing available porosity
for bone ingrowth. Preliminary in vivo results provided evidence of bone ingrowth into the
pore network, which could lead to enhanced implant stabilization. Though the cubic
morphology of ingrown bone produced by this technique provides convincing preliminary
evidence of improved osseointegration, the functionality of bone ingrowth remains to be
determined in future studies.
Acknowledgements
This work was supported by Solvay Advanced Polymers. The authors would like to thank K. Poynter and H. Harris
for their assistance in the mechanical characterization and Laura Gartner for her assistance regarding SEM imaging.
N.T.E., D.C.W., D.L.S., and K.G. are inventors of the technology disclosed in this manuscript. The technology
disclosed in this manuscript has been licensed from Georgia Tech Research Corporation. N.T.E is supported by the
National Science Foundation Graduate Research Fellowship under Grant No. 2013162284. F.B.T. is supported by
the TI:GER program at Georgia Institute of Technology.
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Fig. 1.
Schematic of the PEEK-SP cross-sectional areas used in stress calculations. The processing
increases cross-sectional areas due to the creation of pores. However, the load-bearing area,
ALB, is representative of the initial area of PEEK material, assuming volume conservation.
The total area, AT, is the sum of the load-bearing area and the area of the pore network,
APORE.

Fig. 2.
Microstructural characterization of PEEK-SP: (a) µCT reconstruction of PEEK-SP structure
showing representative pore layer cross-section. Note the cubic pore morphology due to
cubic sodium chloride crystals. Scale bar is 1 mm. (b) Strut spacing histogram as
characterized by micro-CT. (c,d) SEM micrographs of the PEEK-SP pore network. Images
confirm cubic pore morphology and pore interconnectivity detected by µCT.

Fig. 3.
Representative stress-strain curves of solid PEEK and PEEK-SP calculated using both ALB
and AT.

Fig. 4.
S-N curve comparing the fatigue behavior of PEEK-SP using the load-bearing, ALB, and the
total area, AT, to solid PEEK, PMMA, and bulk porous tantalum tested by another group
[39]. Arrows denote tests that were halted after reaching 106 cycles (solid PEEK, PEEK-
SP), which is defined as the runout stress.

Fig. 5.
Interfacial shear strength of PEEK-SP compared to smooth PEEK and sintered PEEK-BP
with the shear strength of trabecular bone shown in the shaded region [48]. Asterisks (*)
indicate p < 0.05.

Fig. 6.
µCT reconstructions of bone growth into PEEK-SP and adjacent to smooth PEEK surfaces
(dashed boxes) at 6 and 12 weeks show the extent of bone ingrowth. Images are oriented
with the lateral side on top. Insets show magnified views of ingrown bone. PEEK implants
are not depicted due to thresholding difficulties of µCT reconstructions. An angled view is
presented to visualize the extent of bone intrusion into the porous surface layer. Note the
cubic morphology of bone in the surface porous PEEK samples, suggesting complete growth
into the cubic pores. Scale bars on µCT images are 1 mm.

Fig. 7.
Bone ingrowth of PEEK-SP and smooth PEEK surfaces: (a,c) Representative histological
images of fibrous tissue formation on smooth PEEK faces at six and twelve weeks,
respectively. (b,d) Representative histological images of bone ingrowth within PEEK-SP
faces at six and twelve weeks, respectively. Osteoid stained deep red; mineralized bone
stained green; fibrous tissue stained light orange; and PEEK material is seen in brown. (e,f)
Representative mineral attenuation maps from µCT at approximately the same cross sections

as (c,d). Blue represents lower mineral density and red indicates high mineral density. Scale
bar is 200 µm.

Fig. 8.
Ashby plot of elastic moduli and ultimate strengths for several orthopaedic biomaterials and
bone that have been reported in the literature [3, 20, 33–38]. Solid-filled ellipses represent
fully dense materials and porous-filled ellipses represent porous materials. While cortical
bone does possess low porosity, it is grouped with the fully dense materials for this
comparison. Each material, with the exception of porous tantalum and polyether-ketone-
ketone (PEKK), has both solid and porous properties included to illustrate the reduction in
properties due to porosity. PEEK-SP is indicated by a porous layer outlining the solid-filled
circle. Superscript ‘t’ refers to materials tested in tension and ‘c’ indicates compression.
Daggers (†) indicate yield strengths where ultimate strength was not reported. Pound signs
(#) indicate bending modulus when elastic modulus was not reported. Asterisks (*) indicate
values tested by our group. Ellipse central location and size represents reported mean and
plus or minus one standard deviation, respectively, where available.

Table 1
Molecular weight distribution.

Mn (g/mol) Mw (g/mol) PDId
Porousa 44 753 100 032 2.24
Solidb 45 717 99 449 2.18
Injection Moldedc 46 208 98 846 2.14
a
Porous region of PEEK-SP
b
Solid region of PEEK-SP
c
Injection molded PEEK without surface porous treatment
d
Polydispersity index, PDI = Mw/Mn

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Acta Biomater. 2015 February ; 13: 159–167. doi:10.1016/j.actbio.2014.11.030.

High strength, surface porous polyether-ether-ketone for load-

Institute of Technology, Atlanta, GA 30332

© 2014 Elsevier Ltd. All rights reserved.

As a relatively new implant material, polyether-ether-ketone (PEEK) has gained widespread

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

2. Materials and Methods

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

2.2 Pore Layer Characterization

To detect changes in molecular weight due to PEEK-SP processing, gel permeation

chromatography (GPC) was performed by Solvay Advanced Polymers on 100 mg samples

2.3 Monotonic and Fatigue Tensile Testing

greater than 1,000,000 cycles unless noted otherwise.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

2.4 Aligned Interfacial Shear

2.5 Preliminary in vivo Animal Study

2.5.2 Ex vivo µCT Imaging—Following euthanization, µCT scans were performed to

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

2.6 Statistical Analysis

3.2 Tensile Monotonic Testing

3.3 Tensile Fatigue Testing

3.4 Aligned Interfacial Shear

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

3.5 Implant Osseointegration

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

The process of creating a surface porosity on PEEK implants introduces a random,

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

lack the strength, ductility and fatigue resistance of PEEK-SP.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

biomaterials & functional materials. 2013; 11:e35–e44. [PubMed: 23413130]

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

osseointegration, and bioactivity of three-dimensional porous and nanostructured network on

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

50. Nieminen T, Kallela I, Wuolijoki E, Kainulainen H, Hiidenheimo I, Rantala I. Amorphous and

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

Molecular weight distribution.

Mn (g/mol) Mw (g/mol) PDId

Porousa 44 753 100 032 2.24

Solidb 45 717 99 449 2.18

Injection Moldedc 46 208 98 846 2.14

Acta Biomater. Author manuscript; available in PMC 2016 February 01.

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